EP0105451B1 - Durch Laser bedruckbare Poly(arylensulfid)-Mischungen - Google Patents

Durch Laser bedruckbare Poly(arylensulfid)-Mischungen Download PDF

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Publication number
EP0105451B1
EP0105451B1 EP83109626A EP83109626A EP0105451B1 EP 0105451 B1 EP0105451 B1 EP 0105451B1 EP 83109626 A EP83109626 A EP 83109626A EP 83109626 A EP83109626 A EP 83109626A EP 0105451 B1 EP0105451 B1 EP 0105451B1
Authority
EP
European Patent Office
Prior art keywords
composition
article
parts
encapsulated
polyarylene sulfide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83109626A
Other languages
English (en)
French (fr)
Other versions
EP0105451A2 (de
EP0105451A3 (en
Inventor
Donald Gene Needham
John Everard Leland
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phillips Petroleum Co
Original Assignee
Phillips Petroleum Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=23704530&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0105451(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Priority to AT83109626T priority Critical patent/ATE33030T1/de
Publication of EP0105451A2 publication Critical patent/EP0105451A2/de
Publication of EP0105451A3 publication Critical patent/EP0105451A3/en
Application granted granted Critical
Publication of EP0105451B1 publication Critical patent/EP0105451B1/de
Expired legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
    • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins

Definitions

  • Polyphenylene sulfide is a plastic which, due to its stability at high temperatures and its resistance against various chemicals, has found ever broadening areas of applications. Among these applications are the use of polyarylene sulfide as an encapsulating material for electrical circuits or other electrical elements, particularly in view of the outstanding electrical properties of polyarylene sulfide.
  • Laser printing is a technique that had been developed for permanent printing on certain surfaces.
  • Another object of this invention is to provide a composition that furnishes a surface which can be printed by exposure to laser beams resulting in relatively high contrast prints on the surface.
  • Yet another object of this invention is to provide a process to produce an electric element encapsulated in polyarylene sulfide.
  • composition and an encapsulation process as defined in the claims are provided.
  • the encapsulated article is laser-printable.
  • the surfaces to be laser printed on are preferably polyarylene sulfide molded articles.
  • molded includes injection molding, extrusion, pultruded, vacuum formed; cast, blowmolded, rotational molded, etc.
  • a composition which comprises the following ingredients the broad ranges represent the ranges within which the composition should be confined in order to obtain good results, the preferred ranges are preferred because they define a composition possessing the physical, chemical and electrical properties best suited for its intended encapsulation purposes:
  • the corrosion inhibitor is optional in the composition but may be added to provide mold and encapsulated component protection.
  • uncured or partially cured poly(arylene sulfide) whether homopolymer, copolymer, terpolymer, and the like, or a blend of such polymers, can be used in the practice of the invention.
  • the uncured or partially cured polymer is a polymer the molecular weight of which can be increased by either lengthening of a molecular chain or by crosslinking or by combination of both by supplying thereto sufficient energy, such as heat.
  • Suitable poly(arylene sulfide) polymers include, but are not limited to, those described in U.S. 3,354,129.
  • poly(arylene sulfide) polymers suitable for purposes of the invention include poly(2,4-tolylene sulfide), poly(4,4'-biphenylene sulfide) and poly(phenylene sulfide). Because of its availability and .desirable properties (such as high chemical resistance, nonflammability, and high strength and hardness) poly(phenylene sulfide) is the presently. preferred poly(arylene sulfide). Various poly(arylene sulfides) are commercially available under the trademark Ryton@ from Phillips Petroleum Company, Bartlesville, Oklahoma.
  • the six print compounds useful in accordance with this invention to provide laser printable polyarylene sulfide compositions are commercially available products. The following tabulation gives a supplier and trademark for each of the print compounds.
  • Typical fillers include fiberglass, talc, titanium dioxide, silica and calcium sulfate. Most preferably the composition of this invention contains one or more of the fillers fiberglass, talc and titanium dioxide.
  • the composition comprises a poly(arylene sulfide) (such as, for example, a poly(phenylene sulfide) and at least one mercaptosilane, such as, for example, the preferred 3-mercaptopropyltrimethoxysilane.
  • a poly(arylene sulfide) such as, for example, a poly(phenylene sulfide)
  • at least one mercaptosilane such as, for example, the preferred 3-mercaptopropyltrimethoxysilane.
  • This silane is preferred because of its extraordinary utility as a coupling agent.
  • composition of this invention optionally contains other additives such as processing aids (e.g. mold release agents), corrosion inhibitors, and stabilizers. It is presently preferred to incorporate a mold release agent into the composition of this invention, particularly when the composition is intended for molding, e.g. in an encapsulation operation. Polyethylene and zinc stearate are examples of useful mold release agents. Corrosion inhibitors are also advantageously contained in the composition, particularly when this composition is used in molding operations such as encapsulation. An example of a corrosion inhibitor is lithium carbonate.
  • composition of this invention is preferably in the form of a powder or in a form of pellets.
  • the ingredients are most preferably dry blended and then extruded into pellets or otherwise molten and converted into powder.
  • the melting or extrusion is carried out at temperatures above the melting point of the polyarylene sulfide and usually at a temperature in the range of about 288 to 343°C (550 to 650°F).
  • a surface of a molded composition as defined above is exposed to a pattern of laser radiation such as to change the irradiated surface as compared to the non-irradiated surface and to generate a preferably visible mark corresponding to the pattern of irradiation on the surface.
  • a laser printer, Laser Mark 920 was used as described in the example and is commercially available from Lumonics, Inc., - Kanata, Canada.
  • the pattern is generated by passing the laser radiation through a stencil.
  • the exposure time is usually short, in the order of microseconds and the depth of the material affected is small, usually in the order of a niil (0,0254 mm) or less.using a power range of the laser on the order of 1-10 joules, preferably 3 joules over an area of about 0.202 CM 2 (0.03125 sq. inches).
  • the specific print compounds used in the compositions of this invention which cause laser printability with good contrast may involve different mechanisms such as mechanical and/or chemical changes in the composition near the surface. Applicants do not wish to be bound, however, by any such theory. It should be understood that good contrast is a matter of interpretation and may comprise a light pigmented resin composition which changes to dark areas under laser exposure or vice versa.
  • the resin color may initially be changed to a lighter color such as at 3 joules energy then to a darker color such as at 10 joules energy.
  • the initial resin pigmentation or color is also based on pigments concentrations and resin formulations which can vary over a wide range.
  • compositions of this invention are for encapsulation of electrical elements, such as integrated circuits, capacitors, resistor networks, and the like.
  • This encapsulation is achieved by flowing the composition of this invention as a melt in a mold over the electric element to be encapsulated while protecting the connecting leads from being coated.
  • the molten composition is allowed to solidify in the mold and then the encapsulated element is removed from the mold.
  • an encapsulated electrical element is produced which can readily and readably be printed upon with laser radiation. It is within the scope of this invention to carry out the laser printing following the encapsulation and most preferably directly in the mold prior to removal of the encapsulated element.
  • the encapsulation steps are generally carried out by injecting the composition of this invention into the mold containing the electrical elements.
  • the temperature for this step will be preferably in the range of 302 to 357°C (575 to 675°F), and also based on the electrical component being encapsulated but it will be sufficiently above the melting point of the polyarylene sulfide to allow adequate flow of the composition into the mold and around the electrical element or elements.
  • the viscosity of the composition used for encapsulation of active components should not exceed about 800 poise. Encapsulation of active electronic components with compositions having viscosities in excess of about 80 Pa . s can cause damage to the components. It is contemplated that the viscosity of the composition will generally range from about 15 to about 50 Pa . s for active components other than very delicate component such as, for example, integrated circuits with wire leads. With respect to very delicate components such as, for example integrated circuits with wire leads the viscosity of the encapsulation composition should be below about 15 Pa s. Encapsulation of integrated circuits with compositions any higher in viscosity can cause wire wash (i.e., breaking of the wires of the integrated circuit). It is contemplated that the viscosity of the composition for the encapsulation of such integrated circuits and the like will generally range from about 7,5 to about 15 Pa. s.
  • viscosity of the composition depends on a number of factors, to obtain composition viscosities below about 80 Pa - s the viscosity of the poly(arylene sulfide) contemplated in encapsulation of active components should generally not exceed about 13 Pa - s. It is contemplated that the viscosity of the poly(arylene sulfide) will, in most applications, range up to about 7 Pa - s. To obtain composition viscosities within the desired range for delicate active components such as, for example, integrated circuits with wire leads the viscosity of the poly(arylene sulfide) should generally be less than about 2,5 Pa ⁇ s.
  • the viscosity of the composition used for encapsulation of passive components should not exceed about 120 Pa - s. Encapsulation of passive electronic components with compositions having viscosities in excess of about 120 Pa ⁇ s can cause damage to the components. It is contemplated that the viscosity of the composition will generally range from about 50 to about 80 Pa ⁇ s.
  • the viscosity of the poly(arylene sulfide) contemplated in encapsulation of passive components should not exceed about 30 Pa . s. It is contemplated that the viscosity of the poly(arylene sulfide) will generally range from about 19 to about 30 Fa ⁇ s.
  • the viscosities mentioned above are determined on a capillary rheometer at 343°C (650°F) and at a shear rate of 1000 sec -1 .
  • the color of the composition was golden yellow.
  • the pellets were used to encapsulate electric circuits . with satisfactory results.
  • Laser printing of the encapsulated circuit resulted in markings having a purplish color with good contrast.
  • chromium oxide green blended in accordance with example 1 recipe in place of ingredient 5 and at a 1 weight percent concentration when exposed to 3 joules laser energy resulted in poor contrast.
  • the chromium oxide is commercially available from Pfizer Co. under the pigment number G4099.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Claims (6)

1. Zusammensetzung enthaltend:
(a) Polyarylensulfid und
(b) mindestens eine Druckverbindung, ausgewählt aus der Gruppe
Monoazo-Nickel-Komplex, nämlich Farbe #12775, Pigmentgrün 10
Bleichromat-Bleimolybdat
Quinacridon, nämlich C. I. Pigment violett 19
Nickel-Antimon-Titan
Kobalt-Zink-Siliciumdioxid
Bleichromat
2. Zusammensetzung nach Anspruch 1, gekennzeichnet durch die folgenden Bestandteile in Gewichtsteilen
(a) Polyarylensulfid, 100 Teile,
(b) Druckverbindung, 0,9 bis 12 Teile,
(c) Füllstoff, 140 bis 220 Teile,
(d) Kupplungsmittel, 0,7 bis 6 Teile,
(e) Verarbeitungshilfsstoff, 0,3 bis 3 Teile,
(f) Korrosionsinhibitor, 0 bis 6 Teile.
3. Verbindung der in Anspruch 1 oder 2 definierten Zusammensetzung zur Herstellung von geformten oder verkapselten Gegenständen, die gewünschtenfalls auf ihre Oberfläche einen Laserdruck enthalten.
4. Verfahren zum Verkapseln eines Gegenstandes, dadurch gekennzeichnet, daß die Verkapselung durchgeführt wird durch
(1) Schmelzen einer in Anspruch 1 oder 2 definierten Zusammensetzung
(2) Verpritzen der so geschmolzenen Zusammensetzung um den zu verkapselnden Gegenstand.
(3) Kühlen der Zusammensetzung, die den zu verkapselnden Gegenstand umgibt und Verfestigen der geschmolzenen Zusammensetzung zur Bildung des verkapselnden Gegenstandes.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der Gegenstand ausgewählt wird aus elektrischen Schaltkreisen und Elementen, und daß die elektrische Verbindung oder die elektrischen Verbindungen des Gegenstandes davor geschützt werden, von der Zusammensetzung bedeckt zu werden.
6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß man den Gegenstand in einer Spritzform anordnet und die geschmolzene Zusammensetzung in die Spritzform einspritzt.
EP83109626A 1982-09-30 1983-09-27 Durch Laser bedruckbare Poly(arylensulfid)-Mischungen Expired EP0105451B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83109626T ATE33030T1 (de) 1982-09-30 1983-09-27 Durch laser bedruckbare poly(arylensulfid)mischungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US429738 1982-09-30
US06/429,738 US4443571A (en) 1982-09-30 1982-09-30 Laser printable polyarylene sulfide compositions

Publications (3)

Publication Number Publication Date
EP0105451A2 EP0105451A2 (de) 1984-04-18
EP0105451A3 EP0105451A3 (en) 1985-07-24
EP0105451B1 true EP0105451B1 (de) 1988-03-16

Family

ID=23704530

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83109626A Expired EP0105451B1 (de) 1982-09-30 1983-09-27 Durch Laser bedruckbare Poly(arylensulfid)-Mischungen

Country Status (7)

Country Link
US (1) US4443571A (de)
EP (1) EP0105451B1 (de)
JP (1) JPS59131652A (de)
AT (1) ATE33030T1 (de)
CA (1) CA1187321A (de)
DE (1) DE3376007D1 (de)
ES (1) ES526096A0 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8293147B2 (en) 2006-08-14 2012-10-23 Chemische Fabrik Budenheim Kg Laser-writable polymer material

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US4680326A (en) * 1985-04-16 1987-07-14 Phillips Petroleum Company Poly(arylene sulfide) composition with improved insulation resistance and cracking resistance
GB2174063B (en) * 1985-04-22 1988-08-17 Philips Electronic Associated Semiconductor device having a laser printable envelope
US4737240A (en) * 1985-05-02 1988-04-12 Ciba-Geigy Corporation Trisazo black dyes from 2-(4'-aminophenylazo)-7-amino-1-naphthol-3-sulfonic acid
FR2583564B1 (fr) * 1985-06-18 1988-06-17 Europ Composants Electron Resine d'enrobage pour marquage thermique.
IT1239577B (it) * 1990-05-14 1993-11-08 Onorato Fedon Metodo per la colorazione di oggetti in genere mediante il trasferimento del colore da un supporto preottenuto
WO1994011664A1 (en) * 1992-11-13 1994-05-26 Mobil Oil Corporation Corrosion resistant connection for use with tubular members
US6028134A (en) * 1995-07-12 2000-02-22 Teijin Limited Thermoplastic resin composition having laser marking ability
EP0753536B1 (de) * 1995-07-13 2000-05-10 Teijin Limited Mit Laser beschriftbare thermoplastische Harzzusammensetzung
US7171053B2 (en) * 2001-03-05 2007-01-30 Koninklijke Philips Electronics N.V. Device and method for compressing a signal
DK1657072T6 (en) 2001-03-16 2016-12-19 Datalase Ltd Method of providing an image by laser
US8048605B2 (en) 2001-03-16 2011-11-01 Datalase Ltd Laser-markable compositions
DE102004050479A1 (de) 2004-10-15 2006-04-27 Chemische Fabrik Budenheim Kg Formmasse für die Herstellung schwer entflammbarer Gegenstände, Pigment hierfür und dessen Verwendung
DE102004050480A1 (de) 2004-10-15 2006-04-27 Chemische Fabrik Budenheim Kg Pigment für laserbeschriftbare Kunststoffe und dessen Verwendung
DE102004050557B4 (de) 2004-10-15 2010-08-12 Ticona Gmbh Lasermarkierbare Formmassen und daraus erhältliche Produkte und Verfahren zur Lasermarkierung
JP4887703B2 (ja) 2005-09-15 2012-02-29 トヨタ自動車株式会社 車両用伝達トルク制限装置
US8196523B2 (en) 2009-05-05 2012-06-12 Parker-Hannifin Corporation Railroad tanker car manway cover seal
JP5577695B2 (ja) * 2009-12-24 2014-08-27 Ｄｉｃ株式会社 ポリアリーレンスルフィド樹脂成形体の製造方法
JP2017180557A (ja) * 2016-03-29 2017-10-05 武蔵精密工業株式会社 伝動装置
DE102016210160A1 (de) 2016-06-08 2017-12-14 Weilburger Coatings Gmbh Wässrige Zusammensetzung zur Erzeugung einer lasermarkierbaren Beschichtung und lasermarkierte Beschichtung
DE102016219858A1 (de) 2016-10-12 2018-04-12 Weilburger Coatings Gmbh Verfahren zur Herstellung einer Beschichtung mit Markierungen auf einer Oberfläche oder einem Teil einer Oberfläche eines Gegenstandes

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8293147B2 (en) 2006-08-14 2012-10-23 Chemische Fabrik Budenheim Kg Laser-writable polymer material

Also Published As

Publication number Publication date
ATE33030T1 (de) 1988-04-15
ES8406946A1 (es) 1984-08-16
US4443571A (en) 1984-04-17
EP0105451A2 (de) 1984-04-18
JPS59131652A (ja) 1984-07-28
EP0105451A3 (en) 1985-07-24
JPH0124417B2 (de) 1989-05-11
ES526096A0 (es) 1984-08-16
CA1187321A (en) 1985-05-21
DE3376007D1 (de) 1988-04-21

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